Method for producing fulvene metal complexes

Abstract

The present invention relates to a process for the preparation of fulvene complexes, and their use as catalysts for the polymerization of unsaturated compounds.

What is claimed is:  
     
       1. Process for the preparation of fulvene-metal complexes of the formula (Ia)                    
       or of the formula (Ib)                    
       wherein 
       M is a metal from group IIIb, IVb, Vb or VIb or the lanthanides or the actinides of the periodic table of the elements according to IUPAC,  
       A denotes an anionic ligand optionally with one or more bridges,  
       X denotes a hydrogen atom, a C 1 - to C 10 -alkyl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 10 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a silyl group substituted by C 1 - to C 10 -hydrocarbon radicals, a halogen atom or an amide of the formula NR 7   2 ,  
       L denotes a neutral ligand,  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are identical or different and represent hydrogen, halogen, a cyano group, a C 1 - to C 20 -alkyl group, a C 1 - to C 10 -fluoroalkyl group, a C 6 - to C 10 -fluoroaryl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 20 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a C 2 - to C 10 -alkenyl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals, a sulfide group substituted by a C 1 -C 10 -hydrocarbon radical or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals, or  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in each case together with the atoms connecting them, form one or more aliphatic or aromatic ring systems, which optionally contain one or more heteroatoms (O, N, S) and 5 to 10 carbon atoms,  
       R 7  represents hydrogen, a C 1 - to C 20 -alkyl group, a C 6 - to C 20 -aryl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
       m, p represent the numbers 0, 1, 2, 3 or 4, which result from the valency and the bonding state of M, and  
       k represents the number 1, 2 or 3, and the sum of k+m+p is 1 to 5, depending on the oxidation level of M, and  
       n is a number from 0 to 10,  
       by reaction of a transition metal compound of the formula (IIa) or (IIb) 
        A m X s M  (IIa) 
       or 
       
         
           A m X s L n M  (IIb)  
         
       
       wherein 
       A, X, L, M, m, and n have the abovementioned meaning and  
       s is 2, 3, 4, 5 or 6 an s is >p,  
       with a fulvene compound of the formula (III)                    
       wherein 
       R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the abovementioned meaning,  
       in the presence of a reducing agent. 
     
     
       2. Process according to  claim 1 , characterized in that the reaction is carried out in a suitable reaction medium at temperatures of −100 to +250° C. 
     
     
       3. Process according to  claim 1 , characterized in that alkali metals, alkaline earth metals or lithium-alkyls are used as the reducing agent. 
     
     
       4. Process according to  claim 1 , characterized in that the reaction is carried out in a solvent. 
     
     
       5. Process according to  claim 4 , characterized in that the reaction is carried out in an ether. 
     
     
       6. Fulvene-metal complexes comprising the formula (Ia)                    
       or of the formula (Ib)                    
       wherein 
       A denotes an anionic ligand optionally with one or more bridges, with the exception of cyclopentadienyl ligands  
       X denotes a hydrogen atom, a C 1 - to C 10 -alkyl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 10 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a silyl group substituted by C 1 - to C 10 -hydrocarbon radicals, a halogen atom or an amide of the formula NR 7   2 ,  
       L denotes a neutral ligand,  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are identical or different and represent hydrogen, halogen, a cyano group, a C 1 - to C 20 -alkyl group, a C 1 - to C 10 -fluoroalkyl group, a C 6 - to C 10 -fluoroaryl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 20 - aryl group, a C 6 - to C 10 -aryloxy group, C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a C 2 - to C 10 -alkenyl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals, a sulfide group substituted by a C 1 -C 10 -hydrocarbon radical or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals, or  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in each case together with the atoms connecting them, form one or more aliphatic or aromatic ring systems, which can contain one or more heteroatoms (O, N, S) and 5 to 10 carbon atoms,  
       R 7  represents hydrogen, a C 1 - to C 20 -alkyl group, a C 6 - to C 20 -aryl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
       m, p represent the numbers 0, 1, 2, 3 or 4, which result from the valency and the bonding state of M, and  
       n is a number from 0 to 10,  
       M is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,  
       k is 1; with the exception of the compounds of the formula (Ia) or (Ib) wherein  
       R 1  and R 2  represent hydrogen and at the same time R 3 , R 4 , R 5  and R 6  represent a methyl group and at the same time A denotes a pentamethylcyclopentadienyl group or a carboranediyl group of the formula C 2 B 9 11 11 .  
     
     
       7. A catalyst system comprising: 
       a) a fulvene metal complex of the formula (Ia)                    
        or of the formula (Ib)                    
        wherein  
       A denotes an anionic ligand optionally with one or more bridges,  
       X denotes a hydrogen atom, a C 1 - to C 10 -alkyl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 10 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10  -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a silyl group substituted by C 1 - to C 10 -hydrocarbon radicals, a halogen atom or an amide of the formula NR 7   2 ,  
       L denotes a neutral ligand,  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are identical or different and represent hydrogen, halogen, a cyano group, a C 1 - to C 20 -alkyl group, a C 1 - to C 10 -fluoroalkyl group, a C 6 - to C 10 -fluoroaryl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 20 - aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a C 2 - to C 10 -alkenyl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals, a sulfide group substituted by a C 1 -C 10 -hydrocarbon radical or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals, or  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in each case together with the atoms connecting them, form one or more aliphatic or aromatic ring systems, which can contain one or more heteroatoms (O, N, S) and 5 to 10 carbon atoms,  
       R 7  represents hydrogen, a C 1 - to C 20 -alkyl group, a C 6 - to C 20 -aryl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
       m, p represent the numbers 0, 1, 2, 3 or 4, which result from the valency and the bonding state of M, and 
       n is a number from 0 to 10,  
       wherein M is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,  
       K is 1 and  
       b) a cocatalyst suitable for activating the metal complex a), the molar ratio of component a) to component b) being in the range from 1:0.1 to 1:10,000.  
     
     
       8. The polymerization of olefins and/or dienes comprising a catalyst system 
       a) a fulvene metal complex of the formula (Ia)                    
        or of the formula (Ib)                    
        wherein  
       A denotes an anionic ligand optionally with one or more bridges,  
       X denotes a hydrogen atom, a C 1 - to C 10 -alkyl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 10 -aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a silyl group substituted by C 1 - to C 10 -hydrocarbon radicals, a halogen atom or an amide of the formula NR 7   2 ,  
       L denotes a neutral ligand,  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are identical or different and represent hydrogen, halogen, a cyano group, a C 1 - to C 20 -alkyl group, a C 1 - to C 10 -fluoroalkyl group, a C 6 - to C 10 -fluoroaryl group, a C 1 - to C 10 -alkoxy group, a C 6 - to C 20 - aryl group, a C 6 - to C 10 -aryloxy group, a C 2 - to C 10 -alkenyl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a C 8 - to C 40 -arylalkenyl group, a C 2 - to C 10 -alkenyl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals, a sulfide group substituted by a C 1 -C 10 -hydrocarbon radical or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals, or  
       R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , in each case together with the atoms connecting them, form one or more aliphatic or aromatic ring systems, which can contain one or more heteroatoms (O, N, S) and 5 to 10 carbon atoms,  
       R 7  represents hydrogen, a C 1 - to C 20 -alkyl group, a C 6 - to C 20 -aryl group, a C 7 - to C 40 -arylalkyl group, a C 7 - to C 40 -alkylaryl group, a silyl group substituted by C 1 -C 10 -hydrocarbon radicals or an amino group which is optionally substituted by C 1 -C 20 -hydrocarbon radicals,  
       m, p represent the numbers 0, 1, 2, 3 or 4, which result from the valency and the bonding state of M, and  
       n is a number from 0 to 10,  
       wherein M is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium,  
       K is 1 and  
       b) a cocatalyst suitable for activating the metal complex a), the molar ratio of component a) to component b) being in the range from 1:0.1 to 1:10,000.